A high-voltage and stable zinc-air battery enabled by dual-hydrophobic-induced proton shuttle shielding

Rechargeable zinc-air batteries (ZABs) stand out among next-generation battery technologies due to their high energy density and high safety but suffer from electrochemical irreversibility. Herein, we report a hybrid ZAB with a long lifespan and high working voltage; it uses a neutral anolyte, an acidic catholyte, and a proton-shuttle-shielding dual-hydrophobic membrane to isolate the two electrolytes. The hybrid ZAB operates through the stable electrochemical plating and stripping of zinc (Zn) in a neutral anolyte and a high-voltage O2 redox reaction in acidic catholyte. The designed proton-shuttle-shielding dual-hydrophobic membrane selectively transports hydrophobic bis(trifluoromethylsulfonyl)imide anions (TFSI−) and effectively avoids the crossover of protons. As a result, the hybrid ZAB exhibits a high working voltage (1.50 V) and stable operation (up to 2,000.0 h) in ambient air. This strategy not only overcomes the severe irreversibility of conventional ZABs but also promotes development of electrolyte-decoupled systems.